Process for preparing catalyst component for polymerization of olefins

ABSTRACT

A process for preparing a catalyst component for the polymerization of olefins which comprises the steps of contacting (a) a magnesium dialkoxide soluble in an inert solvent, (b) a silicon compound having the hydrogen-silicon bond, and (c) an electron donor compound with one another in the presence of an inert solvent, and contacting the resulting reaction product with (d) a titanium compound.

This is a continuation division, of application Ser. No. 705,770, filed2/26/85, now U.S. Pat. No. 4,654,318.

FIELD OF THE TECHNOLOGY

The present invention relates to a process for preparing a catalystcomponent for the polymerization of olefins, and more particularly, to aprocess for preparing a catalyst component which provides in high yieldsolefin polymers having superior particle properties and highstereoregularity.

BACKGROUND TECHNOLOGY

There have been proposed many processes for the production of a solidcatalyst component for the polymerization of olefins which is composedessentially of magnesium, titanium, halogen, and an electron donorcompound. The catalyst component produced by these processes has made itpossible to produce in high yields polymers having considerably highstereoregularity. However, there still exists a demand for furtherimprovement.

In the production of olefin polymers, it is important to regulate theparticle shape of the polymer obtained. Recently, there has beenproposed several methods for producing in high yields olefin polymerswhich have high stereoregularity and improved particle properties. Forexample, there is disclosed in U.S. Pat. No. 4,330,649 a process forproducing an olefin polymer by using a catalyst component which isobtained by contacting a liquid magnesium compound having no reducingability, a liquid titanium compound, and an electron donor compoundhaving no active hydrogen with one another in the liquid state. Thisprocess has an advantage over the conventional technology; yet it is notsatisfactory.

There is disclosed in Japanese Patent Laid-open No. 92009/1982 acatalyst component for the polymerization of olefins which is producedby contacting a magnesium compound, an electron donor compound, asilicon compound having the Si-H bond, and a titanium halide with oneanother. The magnesium compound used in the disclosed invention issubstantially insoluble in an inert solvent; therefore, it is impossibleto contact the magnesium compound with an electron donor compound and/orsilicon compound in the liquid state. Thus the resulting catalystcomponent is low in catalytic activity and provides a polymer having lowstereoregularity and unsatisfactory properties.

There is disclosed in Japanese Patent Laid-open No. 36203/1980 acatalyst component which is produced by contacting a hydrocarbon-solubleorganomagnesium component or a reaction product thereof with a complex,with a chlorosilane compound having the Si-H bond, and contacting theresulting solid with a titanium compound and an ester of carboxylicacid. The solic has the Mg-C bond having reducing ability, which is notformed when a magnesium dialkoxide is used in the present invention. Theresulting catalyst component has low catalytic activity and providespolymers having unsatisfactory particle properties.

DISCLOSURE OF THE INVENTION OBJECT OF THE INVENTION

It is an object of this invention to provide a catalyst component whichprovides in high yields olefin polymers having superior particleproperties and high stereoregularity.

The present inventors previously developed and have disclosed in U.S.patent application Ser. No. 481,197, filed Apr. 1, 1983, a catalystcomponent obtained by contacting a magnesium alkoxide, a siliconcompound having the hydrogen-silicon bond, an electron donor compound,and a titanium compound with one another, said catalyst componentproviding in high yields olefin polymers having high stereoregularity.It has now been discovered that the object of this invention can beachieved when the magnesium alkoxide is replaced by a magnesiumdialkoxide soluble in an inert solvent. This finding led to the presentinvention.

SUMMARY OF THE INVENTION

The gist of this invention resides in a process for preparing a catalystcomponent for the polymerization of olefins which comprises the steps ofcontacting (a) a magnesium dialkoxide soluble in an inert solvent, (b) asilicon compound having the hydrogen-silicon bond, and (c) an electrondonor compound with one another in the presence of an inert solvent, andcontacting the resulting reaction product with (d) a titanium compound.

Raw Materials for Preparation of Catalyst Component (A) MagnesiumDialkoxide

The magnesium dialkoxide used in this invention is a compound which issoluble in an inert solvent. By "inert solvent" is meant a which isinactive to a magnesium dialkoxide, a silicon compound having thehydrogen-silicon bond, and/or an electron donor compound when they arecontacted with one another. Usually, it is a hydrocarbon or halogenatedhydrocarbon. Examples of such an inert solvent include saturatedaliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane,dodecane, and tetradecane; saturated alicyclic hydrocarbons such ascyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane,cyclooctane, and cyclodecane; aromatic hydrocarbons such as benzene,toluene, xylene, ethylbenzene, cumene, and cymene; petroleum solventssuch as kerosene; and halogenated hydrocarbons such as carbontetrachloride, dichloroethane, trichloroethane, trichloropropane,dichlorobutane, dichloropentane, dichlorohexane, dichloroctane,dichloropentane, dichlorohexane, dichloroctane, and chlorobenzene.

The magnesium dialkoxide used in this invention is one which is solublein at least one of the above-mentioned inert solvents at normaltemperature. It is represented by the formula Mg(OR)(OR¹), where R andR¹ are the same or different alkyl, cycloalkyl, aryl, alkenyl, oraralkyl groups, preferably alkyl or cycloalkyl group, most suitablealkyl group. Those magnesium dialkoxides having hydrocarbon groups ofcarbon number less than 7 are insoluble in the above-mentioned inertsolvent. Thus it is necessary that the hydrocarbon groups in themagnesium dialkoxide should have a carbon number of at least 7 orgreater and side chains.

Preferred examples of magnesium dialkoxide include magnesiumdi-2-ethylhexyloxide, magnesium di-2-methylhexyloxide, magnesiumdi-2-ethylheptyloxide, magnesium di-2-methylheptyloxide, magnesiumdi-2-ethylpentyloxide, magnesium di-2-(methylethyl)pentyloxide,magnesium di-1-methylhexyloxide, magnesium di-1-ethylpentyloxide,magnesium di-1-propylbutoxide, magnesium di-1-methylheptyloxide,magnesium di-1-ethylhexyloxide, magnesium di-1-propylpentyloxide,magnesium di-1-dimethylpentyloxide, magnesium di-1-dimethylhexyloxide,magnesium di-1-dimethylheptyloxide, magnesium di-1-dimethyloctyloxide,magnesium di-1-methylnonyloxide, magnesium di-1-methylethylbutoxide,magnesium di-1-(methylethyl)pentyloxide, magnesiumdi-1-(methylethyl)hexyloxide, magnesium di-1-(methylethyl)heptyloxide,magnesium di-1-(methylethyl)octyloxide, magnesium di-1-diethylpropoxide,magnesium di-1-diethylpentyloxide, magnesium di-1-diethylhexyloxide,magnesium di-1-diethylheptyloxide, magnesium di-1-diethyloctyloxide,magnesium di-1-(ethylbutyl)pentyloxide, magnesiumdi-1-dibutylpentyloxide, magnesium di-1-methylcyclohexyloxide, magnesiumdi-1-methylcyclohexyloxide, magnesium di-1-methylcyclohexyloxide, andmagnesium di-4-methylcyclohexyloxide. Preferable among them aremagnesium di-2-ethylhexyloxide, magnesium di-1-methylhexyloxide,magnesium di-1-ethylpentyloxide, magnesium di-1-methylheptyloxide, andmagnesium di-1-ethylhexyloxide.

These magnesium alkoxides may be commercial ones or may be prepared byknown methods. For example, they may be prepared by reacting metallicmagnesium or dihydrocarbyl magnesium with an alcohol represented by ROHor R¹ OH (R and R¹ are the same as defined above). Where metallicmagnesium is used, a halogen such as iodine may be added to promote thereaction. They may also be prepared by the alkoxyl group interchangereaction in which a magnesium dialkoxide insoluble in an inert solventis contacted with an alcohol having the same hydrocarbon group as thedesired alkoxide has.

(B) Silicon Compound Any silicon compound having the hydrogen-siliconbond can be used in this invention. It is represented by the formulaH_(m) R'_(n) SiX_(r) where R' is a hydrocarbon group, R"O-(R"=hydrocarbon group), R² R³ N- (R² and R³ =hydrocarbon groups), or R⁴COO- (R⁴ =hydrogen atom or hydrocarbon group); X is a halogen atom; m is1 to 3; 0≦r21 4, and m+n+r=4. The group represented by R' may be thesame or different when n is greater than 1.

The hydrocarbon groups represented by R', R", R¹, R², R³, and R⁴include, for example, alkyl, alkenyl, cycloalkyl, aryl, and aralkyl ofcarbon number 1 to 16. The alkyl group includes methyl, ethyl, propyl,n-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl, and n-decyl. Thealkenyl group includes vinyl, allyl, isopropenyl, propenyl, and butenyl.The cycloalkyl group includes cyclopentyl and cyclohexyl. The aryl groupincludes phenyl, tolyl, and xylyl. The aralkyl group includes benzyl,phenetyl, and phenylpropyl.

Preferable among them are lower alkyl groups such as methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, and t-butyl, and aryl groups suchas phenyl and tolyl.

X in the above formula denotes a halogen atom such as chlorine, bromine,and iodine. Preferable among them is chlorine.

Examples of the silicon compound include HSiCl₃, H₂ SiCl₂, H₃ SiCl, HCH₃SiCl₂, HC₂ H₅ SiCl₂, H(t-C₄ H₉)SiCl₂, HC₆ H₅ SiCl₂, H(CH₃)₂ SiCl, H(i-C₃H₇)₂ SiCl, H₂ C₂ H₅ SiCl, H₂ (n-C₄ H₉)SiCl, H₂ (C₆ H₄ CH₃)SiCl,HSi(CH₃)₃, HSiCH₃ (OCH₃)₂, HSiCH₃ (OC₂ H₅)₂, HSi(OCH₃)₃, (C₂ H₅)₂ SiH₂,HSi(CH₃)₂ (OC₂ H₅), HSi(CH₃)₂ [(CH₃)₂ ], HSiCH₃ (C₂ H₅)₂, HSiC₂ H₅ (OC₂H₅)₂, HSiCH₃ [N(CH₃)₂ ]₂, C₆ H₅ SiH₃, HSi(C₂ H₅)₃, HSi(OC₂ H₅)₃.HSi(CH₃)₂ [N(C₂ H₅)₂ ], HSi[N(CH₃)₂ ]₃, C₆ H₅ CH₃ SiH₂, C₆ H₅ (CH₃)₂SiH, (n-C₃ H₇)₃ SiH, HSiCl(C₆ H₅)₂, H₂ Si(C₆ H₅)₂, HSi(C₆ H₅)₂ CH₃,(n-C₅ H₁₁ O)₃ SiH, HSi(C₆ H₅)₃, and (n-C₅ H₁₁)₃ SiH. Additionalcompounds include (ClCH₂ CH₂ O)₂ CH₃ SiH, HSi(OCH₂ CH₂ Cl)₃, [H (CH₃)₂Si]₂ O, [H(CH₃)₂ Si]₂ NH, (CH₃)₃ SiOSi(CH₃)₂ H, [H(CH₃)₂ Si]₂ C₆H₄,[H(CH₃)₂ SiO₂ ]₂ Si(CH₃)₂, [(CH₃)₃ SiO]₂ SiHCH₃, [(CH₃)₃ SiO]₃ SiH,and [Si(CH₃)(H)O]₅. Preferable among them are those silicon halidecompounds in which R' is a hydrocarbon, n is 0 to 2, and r is 1 to 3, asexemplified by HSiCl₃, H₂ SiCl₂, H₃ SiCl, HCH₃ SiCl₂,HC₂ H₅ SiCl₂,H(t-C₄ H₉)SiCl₂ H₃ SiCl, HCH₃ SiCl₂, HC₂ H₅ SiCl₂, H(t-C₄ H₉) SiCl₂, HC₆H₅ SiCl₂, H(CH₃)₂ SiCl, H(i-C₃ H₇)₂ SiCl, H₂ C₂ H₅ SiCl, H₂ (n-C₄H₉)SiCl, H₂ (C₆ H₄ CH₃)SiCl, and HSiCl(C₆ H₅)₂. Most suitable among themare HSiCl₃, HCH₃ SiCl₂, and H(CH₃)₂ SiCl and especially HSiCl₃.

(C) Electron Donor Compound

The electron donor compound used in this invention includes carboxylicacids, carboxylic acid anhydrides, carboxylate esters, carboxylic acidhalides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes,alcoholates, phosphoamides, thioethers, thioesters, carbonate esters,and compounds of phosphorus, arsenic, or antimony attached to an organicgroup through a carbon or oxygen atom. Preferable among them arecarboxylic acids, carboxylic acid anhydrides, carboxylate esters,halogenated carboxylic acids, alcohols, and ethers.

Examples of the carboxylic acids include aliphatic monocarboxylic acidssuch as formic acid, acetic acid, propionic acid, butyric acid,isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid,methacrylic acid, and crotonic acid; aliphatic dicarboxylic acids suchas malonic acid, succinic acid, glutaric acid, adipic acid, sebacicacid, maleic acid, and fumaric acid; aliphatic oxycarboxylic acids suchas tartaric acid; alicyclic carboxylic acids such as cyclohexanemonocarboxylic acid, cyclohexene monocarboxylic acid,cis-1,2-cyclohexane dicarboxylic acid, andcis-4-methylcyclohexene-1,2-dicarboxylic acid; aromatic monocarboxylicacids such as benzoic acid, toluic acid, anisic acid, p-t-butylbenzoicacid, naphthoic acid, and cinnamic acid; and aromatic dicarboxylic acidssuch as phthalic acid, isophthalic acid, terephthalic acid, andnaphthalic acid.

The carboxylic acid anhydrides are the acid anhydrides of theabove-mentioned carboxylic acids.

The carboxylate esters that can be used are mono- or diesters of theabove-mentioned carboxylic acids. Examples of the carboxylate estersinclude butyl formate, ethyl acetate, butyl acetate, isobutylisobutyrate, propyl pivalate, isobutyl pivalate, ethyl acrylate, methylmethacrylate, ethyl methacrylate, isobutyl methacrylate, diethylmalonate, diisobutyl malonate, diethyl succinate, dibutyl succinate,diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutylglutarate, diisobutyl adipate, dibutyl sebacate, diethyl maleate,dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethylfumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate,diisobutyl tartrate, ethyl cyclohexanecarboxylaten, methyl benzoate,ethyl benzoate, methyl p-toluate, ethyl p-t-butyl benzoate, ethylp-anisate, ethyl alpha-naphthoate, isobutyl alpha-naphthoate, ethylcinnamate, monomethyl phthalate, dibutyl phthalate, diisobutylphthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexylphthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate,isobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate,diethyl naphthalate, and dibutyl naphthalate.

The carboxylic acid halides that can be used are acid halides of theabove-mentioned carboxylic acids. Their examples include acetic acidchloride, acetic acid bromide, acetic acid iodide, propionic acidchloride, butyric acid chloride, butyric acid bromide, butyric acidiodide, pivalic acid chloride, pivalic acid bromide, acrylic acidchloride, acrylic acid bromide, acrylic acid iodide, methacrylic acidchloride, methacrylic acid bromide, methacrylic acid iodide, crotonicacid chloride, malonic acid chloride, malonic acid bromide, succinicacid chloride, succinic acid bromide, glutaric acid chloride, glutaricacid bromide, adipic acid chloride, adipic acid bromide, sebacic acidchloride, sebacic acid bromide, maleic acid chloride, maleic acidbromide, fumaric acid chloride, fumaric acid bromide, tartaric acidchloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride,cyclohexanecarboxylic acid bromide, 1-cyclohexanecarboxylic acidchloride, cis-4-methylcyclohexene carboxylic acid chloride,cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride,benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisicacid chloride, p-anisic acid bromide, alpha-naphthoic acid chloride,cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride,phthalic acid dibromide, isophthalic acid dichloride, isophthalic aciddibromide, terephthalic acid dichloride, and naphthalic acid dichloride.Additional examples include dicarboxylic acid monoalkylhalides such asadipic acid monomethylchloride, maleic acid monoethylchloride, andmaleic acid monomethylchloride.

The alcohols are represented by the formula R⁵ OH, where R⁵ is an alkyl,alkenyl, cycloalkyl, aryl, or aralkyl group of carbon number 1 to 12.Examples of the alcohols include methanol, ethanol, propanol,isopropanol, butanol, isobutanol, pentanol, hexanol, octanol,2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol,cresol, xylenol, ethylphenol, isopropylphenol, p-t-butylphenol, andn-octylphenol.

The ethers are represented by the formula R⁵ OR⁶, where R⁵ and R⁶ arealkyl, alkenyl, cycloalkyl, aryl, or aralkyl groups of carbon number 1to 12, and R⁵ and R⁶ may be the same or different. Their examplesinclude diethyl ether, diisopropyl ether, dibutyl ether, diisobutylether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethylallylether, butylallyl ether, diphenyl ether, anisole, and ethylphenyl ether.

(D) Titanium Compound

The titanium compound used in this invention is a compound of divalent,trivalent, or tetravalent titanium. Examples of these compounds includetitanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium,trichlorobutoxytitanium, dichlorodiethoxytitanium,dichlorodibutoxytitanium, dichlorodiphenoxytitanium,chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium,and titanium trichloride. Preferable among them are tetravalent titaniumhalides such as titanium tetrachloride, trichloroethoxytitanium,dichlorodibutoxytitanium, and dichlorodiphenoxytitanium. Particularlypreferable is titanium tetrachloride.

Preparation of Catalyst Component

The catalyst component used in this invention is obtained by contactinga magnesium alkoxide (component A), a silicon compound having thehydrogen-silicon bond (component B), and an electron donor compound(component C) with one another in the presence of an inert solvent, andcontacting the resulting reaction product with a titanium compound(component D).

(1) Contacting of Components A, B, and C

The contacting of the three components A, B, and C can be accomplishedby (1) contacting component A and component B with each other,contacting the resulting contact product with component C, (2)contacting a mixture of component A and component C with component B,(3) contacting a mixture of component B and component C with componentA, or (4) contacting component A, component B, and component C with oneanother simultaneously. Methods (1) to (3) are preferable. They aredescribed in the following:

Method (1)

The contacting of component A with component B is accomplished bycontacting them with each other in the presence of an inert solvent. Themethod for contacting includes (i) mixing and stirring component A andcomponent B in the presence of an inert solvent, (ii) dropping withstirring a solution of component A in an inert solvent into a systemcontaining component B in the presence or absence of an inert solvent,and (iii) dropping with stirring component B into a solution ofcomponent A in an inert solvent. The method (ii) is preferable. Morethan one kind of inert solvent may be used. The solvent used forpreparing the solution of component A may be different from that usedfor contacting with component B; but they should preferably be of thesame kind.

One mol of component A is contacted with 0.5 to 10 mol, preferably 1 to5 mol, of component B. The contacting is carried out at -80° to 200° C.for 0.5 to 100 hours. Where a solvent solution of component A is droppedinto a system containing component B, it is preferable that the droppingis performed at a temperature below room temperature, particularly at alow temperature in the neighborhood of 0° C., and the temperature israised after the dropping is complete. This method provides a catalystcomponent having improved particle properties. The inert solvent may beused in an amount of 10 ml to 100 liters, preferably 100 ml to 10liters, for 1 mol of component A.

The contact product of component A and component B is then contactedwith component C by mixing and stirring them in the presence of an inertsolvent. The contacting is carried out at 0° to 150° C. for 0.5 to 10hours. The inert solvent is used in an amount of 10 ml to 100 liters,preferably 100 ml to 10 liters, for 1 mol of component A. Component Cshould preferably be used in an amount of 0.005 to 10 gram mol,particularly 0.01 to 1 gram mol, for 1 gram atom of magnesium in thecontact product of component A and component B.

Method (2)

The mixture of component A and component C is contacted with component Bby slowly dropping a solution of component A and component C in an inertsolvent into a system containing component B at a temperature below roomtemperature, particularly at a low temperature in the neighborhood of 0°C., and the temperature is raised after the dropping is complete. Thismethod provides a catalyst component of uniform particle size.

Method (3)

The mixture of component B and component C is contacted with component Aby slowly dropping a solution of component A in an inert solvent into asystem containing component B and component C at a temperature belowroom temperature, particularly at a low temperature in the neighborhoodof 0° C., and the temperature is raised after the dropping is complete.This method provides a catalyst component of uniform particle size.

Component B is used in an amount of 0.5 to 10 mol, preferably 1 to 5mol, and component C is used in an amount of 0.005 to 10 mol, preferably0.01 to 1 mol, for 1 mol of component A. The inert solvent is used in anamount of 10 ml to 100 liters, preferably 100 ml to 10 liters, for 1 molof component A. The contacting is performed at 0° to 200° C. for 0.1 to100 hours excluding the time required for dropping the solution ofcomponent A in an inert solvent.

The reaction product obtained by the above-mentioned methods (1) to (3)is usually a solid. It is then contacted with a titanium compound(component D) after separation or without separation from the reactionsystem. Before contacting with component D, it may be washed with theabove-mentioned solvent, particularly a hydrocarbon, with or withoutheating.

(2) Contacting with Component D

The contact product obtained in the above step (1) (designated ascontact product A) is subsequently contacted with component D. Thecontacting may be accomplished by simply bringing them into contact witheach other; but preferably by mixing and stirring both in the presenceof a hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene,toluene, and xylene.

Component D should be used in an amount of 0.1 gram mol or above,preferably 1 to 50 gram mol, for 1 gram atom of magnesium in the contactproduct A.

The contacting in the presence of a hydrocarbon should be carried out at0° to 200° C. for 0.5 to 20 hours, preferably at 60° to 150° C. for 1 to5 hours.

The contacting with component D should preferably be performed more thanonce. The second contact may be performed in the same way as mentionedabove; but in the case where the first contact is performed in thepresence of a hydrocarbon, the second contact should preferably beperformed after the separation of the hydrocarbon, which may be followedby washing with a hydrocarbon, if required.

The solid substance obtained by the above method is washed, as required,with an inert hydrocarbon such as hexane, heptane, octane, cyclohexane,benzene, toluene, and xylene, followed by drying. Thus there is obtainedthe catalyst component.

The catalyst component obtained as mentioned above is made into acatalyst for the polymerization of olefins by combining it with anorganic compound of Group I - III metals in the Periodic Table.

According to this invention, an organic compound of lithium, magnesium,calcium, zinc, or aluminum can be used. The preferred one is anorganoaluminum compound represented by the formula R_(n) ⁷ AlX_(3-n),where R⁷ is an alkyl or aryl group; X is a halogen atom, alkoxyl group,or hydrogen atom; and n is any number in the range of 1≦n≦3. Preferredones are alkyl aluminum compound and a mixture thereof or complexthereof having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms,such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkylaluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminummonoalkoxide, and dialkyl aluminum monohydride. Examples of suchcompound include trialkyl aluminum such as trimethyl aluminum, triethylaluminum, tripropyl aluminum, triisobutyl aluminum, and trihexylaluminum; dialkyl aluminum monohalide such as dimethyl aluminumchloride, diethyl aluminum chloride, diethyl aluminum bromide, diethylaluminum iodide, and diisobutyl aluminum chloride; monoalkyl aluminumdihalide such as methyl aluminum dichloride, ethyl aluminum dichloride,methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminumdiiodide, and isobutyl aluminum dichloride; alkyl aluminum sesquihalidesuch as ethyl aluminum sesquichloride; dialkyl aluminum monoalkoxidesuch as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethylaluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminumethoxide and diisobutyl aluminum phenoxide; and dialyl aluminum hydridesuch as dimethyl aluminum hydride, diethyl aluminum hydride, dipropylaluminum hydride, and diisobutyl aluminum hydride.

Preferably among them are trialkyl aluminums, and most suitable amongthem are triethyl aluminum and triisobutyl aluminum. These trialkylaluminums may be used in combination with other organoaluminum compoundssuch as commercially available diethyl aluminum chloride, ethyl aluminumdichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, ordiethyl aluminum hydride, or a mixture or a complex thereof.

According to this invention, it is also possible to use anorganoaluminum compound in which two or more aluminum atoms are bondedthrough an oxygen atom or a nitrogen atom. Examples of such compoundsinclude those which are represented by the formulas (C₂ H₅)₂ AlOAl(C₂H₅)₂, (C₄ H₉)₂ AlOAl(C₄ H₉)₂, and (C₂ H₅)₂ AlNC₂ H₅ Al(C₂ H₅)₂.

Organic compound of other metals than aluminum include, for example,diethyl magnesium, ethyl magnesium chloride, diethyl zinc, LiAl(C₂ H₅)₄,and LiAl (C₇ H₁₅)₄.

The organometallic compound is used in an amount of 1 to 2000 gram mol,preferably 10 to 700 gram mol, for 1 gram atom of titanium in thecatalyst component. One or more kinds of organometallic compounds may beused.

The catalyst for olefin polymerization which is composed of the catalystcomponent of this invention and the above-mentioned organometalliccompound may further be combined with an electron donor compound and/oran organosilicon compound.

The electron donor compound for this purpose may be selected from theelectron donor compounds used as component C for the preparation of thecatalyst component of this invention. Preferable among them arecarboxylate esters, alcohols, ethers, and ketones. The electron donorcompound is used in an amount of 0.005 to 1.0 gram mol, preferably 0.01to 0.5 gram mol, for 1 gram atom of metal in the organometalliccompound.

The electron donor compound that can be used also includes a Lewis basehaving the steric hindrance (simply referred to as Lewis basehereinafter). It is a compound having a nitrogen atom or oxygen atom inthe molecule.

Examples of the Lewis base include piperidine compounds such as2,2,6.6-tetramethylpiperidine, 2,6-diisopropylpiperidine,2,6-diisobutylpiperidine, 2,6-diisobutyl-4-methylpiperidine,2,2,6-trimethylpiperidine, 2,2,6,6-tetraethylpiperidine,1,2,2,6,6-pentamethylpiperidine, 2,2,6,6-tetramethyl-4-piperidylbenzoate, and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate; pyridinecompounds such as 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, and2-isopropyl-6-methylpyridine; pyrrolidine compounds such as2,2,5,5-tetramethylpyrrolidine, 2,5-diisopropylpyrrolidine,2,2,5-trimethylpyrrolidine, 1,2,2,5,5-pentamethylpyrrolidine, and2,5-diisobutylpyrrolidine; amine compounds such asdiisopropylethylamine, t-butyldimethylamine, diphenylamine, anddi-o-triethylamine; aniline compounds such as N,N-diethylaniline, andN,N-diisopropylaniline; ketone compounds such as o-tolyl-t-butylketone,methyl-2,6-di-t-butylphenylketone, and di-o-tolylketone; furan compoundssuch as 2,2,5,5-tetraethyltetrahydrofuran, and2,2,5,5-tetramethyltetrahydrofuran; and pyran compounds such as2,2,6,6-tetraethyltetrahydropyran and2,2,6,6-tetramethyltetrahydropyran.

The Lewis base is used in an amount of 0.02 to 2.0 gram mol, preferably0.05 to 0.8 gram mol, for 1 gram atom of metal in the organometalliccompound. One or more kinds of Lewis base may be used. In addition, itmay be combined with an electron donor compound. The combination with anelectron donor compound results in a polymer having improvedstereoregularity.

The organosilicon compound that can be combined with the above-mentionedcatalyst for olefin polymerization is one which is represented by theformula where R_(p) ⁸ SiX_(m) (OR⁹)_(n), where R⁸ and R⁹ are the same ordifferent hydrocarbon groups, X is a halogen atom, 0≦p<4, 0≦m<4, 0<n≦4,and p+m+n=4. The hydrocarbon groups include alkyl, alkenyl, cycloalkyl,aryl, and aralkyl groups. If p is 2 or above, R⁸ may denote hydrocarbongroups of different kind. The halogen atom represented by X shouldpreferably be a chlorine atom.

Examples of the organosilicon compound include tetramethoxysilane,tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane,tetraphenoxysilane, tetra(p-methylphenoxy)silane, tetrabenzyloxysilane,methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane,methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane,ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane,butyltributoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane,vinyltriethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, benzyltriphenoxysilane, methyltriallyloxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane,dimethyldiisopropoxysilane, dimethyldibutoxysilane,dimethyldihexyloxysilane, dimethyldiphenoxysilane,diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane,dibutyldiisopropoxysilane, dibutyldibutoxysilane,dibutyldiphenoxysilane, diisobutyldiethoxysilane,diisobutyldiisobutoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane,divinyldiphenoxysilane, diallyldipropoxysilane,diphenyldiallyloxysilane, methylphenyldimethoxysilane, andchlorophenyldiethoxysilane. Preferable among them areethyltriethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, diphenyldimethoxysilane,methylphenyldimethoxysilane, and chlorophenyldiethoxysilane.

The silicon compound is used in an amount of 0.02 to 2.0 gram mol,preferably 0.05 to 0.8 gram mol, for 1 gram atom of metal in theorganometallic compound. One or more kinds of silicon compound may beused.

The electron donor compound (including Lewis base) and/or theorganosilicon compound may be used simultaneously with the catalystcomponent and organometallic compound, or may be used after thepreliminary contacting with the organometallic compound.

The polymerization catalyst prepared as mentioned above is useful as acatalyst for homopolymerization of monoolefins or copolymerization of amonoolefin with other monoolefin or diolefin. It is particularlysuitable for homopolymerization of alpha-olefin, particularlyalpha-olefin of carbon number 3 to 6 such as propylene, 1-butene,4-methyl-1-pentene, and 1-hexene. It is also suitable for random orblock copolymerization of alpha-olefins or an alpha-olefin and ethylene.In addition, it is useful for homopolymerization of ethylene and forrandom or block copolymerization of ethylene and an alpha-olefin ofcarbon number 3 to 10 as exemplified above.

The polymerization may be performed either in gas phase or liquid phase.The liquid phase polymerization may be accomplished in an inerthydrocarbon such as n-butane, isobutane, n-pentane, isopentane, hexane,heptane, octane, cyclohexane, benzene, toluene, and xylene, or in theliquid monomer. The polymerization temperature is usually -80° C. to+150° C., preferably 40° to 120° C. The polymerization pressure is 1 to60 atm. The molecular weight modification of the resulting polymer isaccomplished in the presence of hydrogen or other known molecular weightmodifier. In the copolymerization of olefins, the quantity of otherolefin to be copolymerized is usually less than 30 wt %, particularly0.3 to 15 wt %, based on the olefin. The polymerization with thecatalyst system of this invention may be performed continuously orbatchwise under the commonly used conditions. The copolymerization maybe performed in one stage or in two stages.

EFFECT OF INVENTION

When applied to polymerization of olefins, particularly alpha-olefins,the catalyst component prepared according to the process of thisinvention provides in high yields olefin polymers having highstereoregularity. The polymer powder thus produced has a high bulkdensity and a narrow particle size distribution.

EXAMPLES

The invention is described in more detail with reference to thefollowing examples and application examples. The scope of this inventionis not limited by the examples. Percent (%) in the examples andapplication examples means wt %, unless otherwise indicated.

The specific surface area (SA) and pore volume (PV) of the catalystcomponent were measured by using Sorptomatic 1810, made by Carlo ErbaCo., Ltd.

The polymerization activity Kc is the quantity (g) of polymer formed pergram of the catalyst component, and the polymerization activity Kt isthe quantity (kg) of polymer formed per gram of titanium in thecatalyst.

The heptane insolubles (abbreviated as H.I.) indicate the ratio ofcrystalline fraction in the polymer and is the quantity of polymer thatremains undissolved when extracted with boiling n-heptane for 6 hours byusing a Soxhlet extractor of improved type. The melt flow rate (MFR) wasmeasured according to ASTM D-1238, and the bulk density was measuredaccording to ASTM D-1895-69, Method A.

EXAMPLE 1 Preparation of Magnesium Dialkoxide

Into a 300-ml flask, with the atmosphere replaced with nitrogen, wascharged 50 ml (32 mmol) of 1% solution of butylethyl magnesium inn-heptane (MAGALA BEM, a product of Texas Alkyls Co., Ltd. in U.S.)Then, a mixture of 10 ml (64 mmol) of 2-ethylhexanol and 20 ml ofheptane was added dropwise with stirring at room temperature over 15minutes. The flask was placed in an oil bath at 120° C., and thereactants were stirred at the reflux temperature of n-heptane for 1 hourto complete the reaction. Thus there was obtained a colorlesstransparent viscous solution of magnesium di-2-ethylhexyloxide (solutionA).

Contacting with Trichlorosilane and Ethyl Benzoate

Into a 300-ml flask, with the atmosphere replaced with nitrogen, werecharged 25 g (180 mmol) of trichlorosilane and 50 ml of n-heptane. Tothis flask was added dropwise a mixture of solution A and 2 ml of ethylbenzoate (14 mmol) with stirring at 0° C. over 1 hour. Upon completionof the dropwise addition, the reaction system was heated to 70° C. andstirring was continued for 6 hours to complete the reaction. Theresulting white solid substance was washed three times with 100 ml ofn-hexane at 65° C. and then twice with 100 ml of toluene at 65° C.

Contacting with Titanium Tetrachloride

To the solid component were added 40 ml of toluene and 60 ml of titaniumtetrachloride, followed by stirring at 90° C. for 2 hours. Thesupernatant liquid was removed by decantation, and 40 ml of toluene and60 ml of titanium tetrachloride were newly added, followed by stirringat 90° C. for 2 hours. The resulting solid substance was filtered off at90° C. and washed with seven 100-ml portions of hexane at 65° C.,followed by drying at 60° C. for 30 minutes under reduced pressure. Thusthere was obtained catalyst component A containing 2.5% of titanium,2.7% of silicon, 19.0% of magnesium, 53.6% of chlorine, and 13.6% ofethyl benzoate. The catalyst component had a specific surface area of190 m² /g and a pore volume of 0.17 cc/g.

EXAMPLE 2 Preparation of Magnesium Dialkoxide

Into a 300-ml glass reactor, with the atmosphere replaced with nitrogen,were charged 0.8 g (33 mmol) of magnesium powder, 100 ml of dodecane, 50mg of iodine, and 10.4 ml (66 mmol) of 2-ethylhexanol, followed bystirring at 145° C. for 10 hours. After the reaction, there was obtaineda colorless transparent viscous solution of magnesiumdi-2-ethylhexyloxide (solution B).

Preparation of Catalyst Component

Solution B was contacted with trichlorosilane, ethyl benzoate, andtitanium tetrachloride in the same way as in Example 1. Thus there wasobtained catalyst component B. Table 1 shows the composition andphysical properties of catalyst component B.

EXAMPLE 3 Preparation of Magnesium Dialkoxide

Into a 300-ml glass reactor equipped with a distillation column, withthe atmosphere replaced with nitrogen, were charged 3.8 g (33 mmol) ofmagnesium diethoxide, 200 ml of n-heptane, and 10.4 ml (66 mmol) of2-ethylhexanol, followed by stirring at 80° C. for 10 hours. During thereaction, about 4 ml of ethanol was distilled away from the distillationcolumn. After the reaction, there was obtained a colorless transparentviscous solution of magnesium di-2-ethylhexyloxide (solution C).

Preparation of Catalyst Component

Solution C was contacted with trichlorosilane, ethyl benzoate, andtitanium tetrachloride in the same way as in Example 1. Thus there wasobtained catalyst component C. Table 1 shows the composition andphysical properties of catalyst component C.

EXAMPLES 4 TO 6

Catalyst components D, E, and F were prepared in the same way as inExamples 1 to 3, respectively, except that ethyl benzoate was replacedby 3.7 ml (14 mmol) of diisobutyl phthalate. Table 1 shows thecomposition and physical properties of these catalyst components.

EXAMPLES 7 AND 8

Catalyst components G and H were prepared in the same way as in Example4, except that trichlorosilane was replaced by 180 mmol ofmethyldichlorosilane (Example 7) and 180 mol of dimethylchlorosilane(Example 8). Table 1 shows the composition and physical properties ofthese catalyst components.

EXAMPLE 9

Into a 300-ml flask, with the atmosphere replaced with nitrogen, werecharged 25 g (180 mmol) of trichlorosilane and 50 ml of n-heptane. Tothis flask was added dropwise with stirring the solution A prepared inExample 1 at 0° C. over 1 hour. After the dropping, the reaction systemwas heated to 70° C. and stirring was continued for 4 hours. Then, 3.7ml (14 mmol) of diisobutyl phthalate was added, and stirring wascontinued at 70° C. for 2 hours. After the reaction, the resulting solidcomponent was washed three times with 100 ml of n-hexane at 65° C. andthen twice with 100 ml of toluene at 65° C. The washed solid componentwas contacted with titanium tetrachloride in the same way as in Example1 to give catalyst component I. Table 1 shows the composition andphysical properties of this catalyst component.

EXAMPLES 10 TO 12

Example 1 was repeated, except that 2-ethylhexanol was replaced by 64mmol each of 2-heptanol, 2-octanol, and 2-methyl-2-hexanol,respectively, to give solution of magnesium di-1-methylhexyloxide,magnesium di-1-methylheptyloxide, and magnesiumdi-1-dimethylpentyloxide, respectively. The magnesium dialkoxidesolutions were contacted with trichlorosilane, diisobutylphthalate andtitanium tetrachloride in the same way was in Example 4 to give catalystcomponents J, K, and L. Table 1 shows the composition and physicalproperties of these catalyst components.

EXAMPLES 13 TO 18

Example 1 was repeated, except that ethyl benzoate was replaced by 14mmol each of benzoic acid anhydride, benzoyl chloride, diethylphthalate, phthalic acid-di-chloride, phthalic acid anhydride, andn-butyl maleate, respectively, to give catalyst components M to R,respectively. Table 1 shows the composition and physical properties ofthese catalyst components.

COMPARATIVE EXAMPLE 1

Into a 300-ml four-neck flask, with the atmosphere replaced withnitrogen, was charged 100 ml of titanium tetrachloride. To this flaskwas added, while keeping the content at 0° C., a mixture of magnesiumdi-2-ethylhexyloxide solution prepared in the same was as in Example 1and 3.7 ml of diisobutyl phthalate, with stirring over 1 hour. Thereaction system was heated to room temperature with stirring over 1 hourand then to 90° C. over 1 hour. Reaction was continued for 2 hours.After the reaction, the supernatant solution was removed by decantation,and 40 ml of toluene and 60 ml of titanium tetrachloride were newlyadded, followed by stirring at 90° C. for 2 hours. The resulting solidsubstance was filtered off at 90° C. and washed with seven 100-mlportions of n-hexane at 65° C., followed by drying at 60° C. for 30minutes under reduced pressure. Thus there was obtained catalystcomponent S containing 5.1% of titanium, 15.5% of magnesium, 43.6% ofchlorine, and 12.9% of diisobutyl phthalate.

COMPARATIVE EXAMPLE 2

Catalyst component T was prepared in the same way as in Example 4,except that trichlorosilane was replaced by tetrachlorosilane Table 1shows the composition and physical properties of the catalyst component.

COMPARATIVE EXAMPLE 3

Into a 300-ml glass reactor, with the atmosphere replaced with nitrogen,was charged 100 ml of 10% solution of butylethyl magnesium in n-heptane.Then, a mixture of 18.2 g of 2-ethylhexanol and 30 ml of n-heptane wasadded with stirring over 15 minutes. Stirring was continued at 80° C.for 2 hours to give a uniform solution. The solution was cooled to roomtemperature, and 1.3 g of phthalic acid anhydride was added. Treatmentwas performed at 100° C. for 1 hour, and the solution was cooled to roomtemperature. Thus there was obtained uniform solution (A).

Into a 500-ml glass reactor, with the atmosphere replaced with nitrogen,was charged 200 ml of titanium tetrachloride and the content was cooledto -20° C. While keeping this temperature, the uniform solution (A) wasadded dropwise with stirring over 1 hour. The reaction system was heatedto 100° C., and 3.9 ml of diisobutyl phthalate was added. Reaction wascarried out at 105° C. for 2 hours. While keeping this temperature, thesupernatant liquid was removed by decantation. 200 ml of titaniumtetrachloride was added, and reaction was carried out at 105° C. for 2hours. After the reaction, the resulting solid substance was filteredoff at 105° C. and washed with seven 250-ml portions of n-hexane at 65°C., followed by drying at 60° C. under reduced pressure. Thus there wasobtained catalyst component U containing 3.0% of titanium, 16.5% ofmagnesium, 56.2% of chlorine, and 10.2% of diisobutyl phthalate.

COMPARATIVE EXAMPLE 4

Into a 400-ml four-neck flask, with the atmosphere replaced withnitrogen, were charged 3.8 g of magnesium diethoxide, 2 ml of ethylbenzoate, and 150 ml of n-heptane. Then, a solution composed of 25 g oftrichlorosilane and 50 ml of n-heptane was added dropwise with stirringat 0° C. over 1 hour. After dropping, the reaction system was heated to70° C. and stirring was continued for 6 hours to complete the reaction.The resulting solid substance was washed three times with 100 ml ofn-hexane at 65° C. and then twice with 100 ml of toluene at 65° C. Thewashed solid substance was contacted with titanium tetrachloride in thesame way as in Example 1 to give catalyst component V having thecomposition as shown in Table 1.

APPLICATION EXAMPLE 1 Polymerization of Propylene

Into a 1.5-liter stainless steel autoclave was charged under thenitrogen atmosphere a mixture formed by mixing, followed by standing for5 minutes, 15 mg of catalyst component A prepared for Example 1, 2 ml ofa solution containing 1 mol of TEAL (triethyl aluminum) in 1 liter ofn-heptane (corresponding to 250 gram atom of aluminum for 1 gram atom oftitanium in catalyst component A), and 1.3 ml of a solution containing0.5 mol of EPA (ethyl p-anisate) in 1 liter of n-heptane (correspondingto 0.33 gram mol of EPA for 1 gram atom of aluminum in TEAL). Then, 750ml of hydrogen as the molecular weight modifier and 1 liter of liquefiedpropylene were forced into the autoclave. The reaction system was heatedto 70° C., and the polymerization of propylene was performed for 1 hour.After polymerization, unreacted propylene was purged. Thus there wasobtained 158 g of white polypropylene powder having an HI of 94.7%, andMFR of 2.5, and a bulk density of 0.38 g/cc. Kc=10,500 and Kt=420. Thepolymer powder had the following particle size distribution:

    ______________________________________                                        840 m above 1.9%   250 m above 15.4%                                          590 m above 1.3%   149 m above 64.0%                                          420 m above 1.3%    53 m above 11.0%                                          350 m above 3.2%    53 m above 1.9%                                           ______________________________________                                    

APPLICATION EXAMPLES 2 AND 3 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Example 1, except that the catalyst component A was replacedby the catalyst component B obtained in Example 2 and the catalystcomponent C obtained in Example 3, respectively. The results are shownin Table 2.

APPLICATION EXAMPLE 4 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Example 1, except that the catalyst component A was replacedby the catalyst component D obtained in Example 4, the EPA solution wasreplaced by PES (phenyltriethoxysilane) solution in n-heptane, with PESbeing 0.1 gram mol for 1 gram atom of aluminum in TEAL, and the volumeof hydrogen gas was changed to 100 ml. The results are shown in Tables 2and 3.

APPLICATION EXAMPLES 5 TO 12 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Example 4, except that the catalyst component D was replacedby the catalyst component E to L obtained in Examples 5 to 12,respectively. The results are shown in Table 2. The particle sizedistribution of the polymer powder obtained in Application Examples 7and 10 is shown in Table 3.

APPLICATION EXAMPLES 13 AND 14 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Example 1, except that the catalyst component A was replacedby the catalyst components M and N obtained in Examples 13 and 14,respectively. The results are shown in Table 2.

APPLICATION EXAMPLES 15 TO 18 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Example 4, except that the catalyst component D was replacedby the catalyst components O to co R obtained in Examples 15 to 18,respectively. The results are shown in Table 2. The particle sizedistribution of the polymer powder obtained in Application Examples 15is shown in Table 3.

APPLICATION EXAMPLES 19 TO 20 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Examples 4 and 7, respectively, except that 12.5 mg each ofcatalyst components D and G were used, 2.4 mmol each of TEAL was used,and PES was replaced by 0.8 mmol each of 2,2,6,6-tetramethyl piperidine.The results are shown in Table 2.

APPLICATION EXAMPLES 21 TO 23 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Example 4, except that the catalyst component D was replacedby catalyst components S to U obtained in Comparative Examples 1 to 3,respectively. The results are shown in Table 2.

APPLICATION EXAMPLE 24 Polymerization of Propylene

The polymerization of propylene was carried out in the same way as inApplication Example 1, except that the catalyst component V obtained inComparative Example 4 was used.

    ______________________________________                                        Kc = 8,700  Kt = 242  HI = 91.5                                               Bulk Density = 0.35   MFR = 2.9                                               ______________________________________                                    

The particle size distribution of the polymer powder is shown in Table3.

APPLICATION EXAMPLE 25 Block Copolymerization of Propylene

Into a 3-liter autoclave, with the atmosphere replaced with nitrogen,were charged 15 mg of catalyst component D, 2.6 mmol of triethylaluminum, and 0.26 mmol of phenyltriethoxysilane. Then, 200 ml ofhydrogen gas and 2 liters of liquefied propylene were added.Homopolymerization was performed with stirring at 70° C. for 1 hour.(The polypropylene was found to have an HI of 96.8% by the analysis ofpolypropylene separately prepared under the same conditions as above.)When the polymerization was complete, unreacted propylene was dischargedand the atmosphere in the autoclave was replaced with nitrogen. Then, amixture gas of ethylene and propylene (ethylene/propylene =1.5 molarratio) was introduced into the autoclave at 1.5 atm. While keeping thispressure, copolymerization was carried out at 70° C. for 3 hours. Whenthe polymerization was complete, unreacted mixture gas was discharged.Thus there was obtained 197 g of propylene block copolymer.

The copolymer portion in the copolymer as calculated from theconsumption of the mixture gas and the quantity of the copolymer formedwas 16.1%. (This is referred to as value C hereinafter.) The ethylenecontent in the copolymer determined by IR spectroscopy was 7.7%. Thismeans that the ethylene content in the copolymer portion is 48%. (Thisis referred to as value G hereinafter.) Calculations from the quantityof the copolymer formed and the consumption of the mixture gas indicatethat 1 g of the catalyst component D formed 13,100 g of propylenehomopolymer (referred to as EH) and 3,500 g of the copolymer portion(referred to as Ec). The MFR of the copolymer was 2 1 g/10 min, and thebulk density was 0.39 g/cc. No fouling occurred in the autoclave, and noagglomeration was found in the polymer particles.

APPLICATION EXAMPLES 26 AND 27 Block Copolymerization of Propylene

The block copolymerization of proplene was carried out in the same wayas in Application Example 25, except that catalyst component D wasreplaced by catalyst component G and catalyst component J, respectively.The results are shown in the following:

    ______________________________________                                        Cata- HI of                                  Ethyl-                           lyst  homo-                                  ene                              comp- poly-                Value Value       con-                             nent  mer     EH      Ec   C     G     MFR   tent                             ______________________________________                                        G     96.7    13,400  3,500                                                                              14.8  50    2.7   7.4                              J     97.0    14,000  3,700                                                                              14.0  49    2.4   6.9                              ______________________________________                                    

APPLICATION EXAMPLE 28 Random Copolymerization of Propylene

The random copolymerization of ethylene and propylene was carried out inthe same way as in Application Example 4, except that 1.5 g of ethylenewas forced into the autoclave in six portions at intervals of 10minutes.

Kc=19,700 and Kt=480. The bulk density of the copolymer was 0.37 g/cc.The ethylene content in the copolymer determined by IR spectroscopy was3.0%. The melting point and crystallization point of the copolymerdetermined by a differential scanning calorimeter were 144° C. and 99°C., respectively.

                  TABLE 1                                                         ______________________________________                                        Exam-  Catalyst  Composition       SA   PV                                    ple    component Ti    Mg   Cl    Si  ED*  m.sup.2 /g                                                                         cc/g                          ______________________________________                                        2      B         2.1   19.1 57.7  2.1 10.5 168  0.14                          3      C         2.4   18.3 59.2  2.5 13.2 172  0.15                          4      D         4.1   15.4 57.3  1.2 18.2 195  0.16                          5      E         3.8   14.5 52.9  1.1 16.1 152  0.14                          6      F         4.5   15.2 49.8  1.1 17.2 170  0.15                          7      G         4.9   14.9 52.0  1.1 16.5 164  0.15                          8      H         3.9   14.8 48.6  1.0 18.1 211  0.19                          9      I         4.5   15.6 49.2  0.8 18.2                                    10     J         4.5   15.2 47.0  0.9 15.2                                    11     K         4.5   14.6 53.6  1.3 16.0                                    12     L         4.6   16.0 50.5  1.1 16.9                                    13     M         2.0   19.2 59.1  2.1 5.9                                     14     N         3.1   17.6 60.5  1.9                                         15     O         4.2   14.8 52.0  1.1 13.2                                    16     P         5.6   14.7 50.8  0.9                                         17     Q         3.9   15.6 53.5  0.8 11.4                                    18     R         3.8   15.4 49.7  1.3 9.8                                      2**   T         5.0   15.1 47.2  0.1 13.6                                     4**   V         3.6   17.6 59.2  0.9 4.6   58  0.06                          ______________________________________                                         *Electron donor compound                                                      **Comparative Examples                                                   

                  TABLE 2                                                         ______________________________________                                        Appli-                                                                              Cata-                                                                   cation                                                                              lyst                         Bulk                                       Exam- compo-  Kc       Kt     HI   density                                                                             MFR                                  ple   nent    (g/g-cat)                                                                              (kg/g-Ti)                                                                            (%)  (g/cc)                                                                              (g/10 min)                           ______________________________________                                         2    B       10,000   476    94.9 0.38  2.0                                   3    C       11,100   462    94.5 0.37  3.1                                   4    D       16,500   402    96.9 0.42  4.2                                   5    E       14,900   392    96.9 0.41  3.8                                   6    F       17,000   378    97.0 0.42  4.3                                   7    G       16,200   330    96.7 0.45  4.2                                   8    H       16,000   410    96.4 0.43  4.5                                   9    I       17,500   389    96.5 0.42  4.2                                  10    J       15,800   351    97.0 0.42  4.1                                  11    K       17,200   382    96.8 0.42  4.9                                  12    L       16,400   357    96.6 0.41  4.7                                  13    M        9,800   490    94.2 0.37  2.1                                  14    N       10,200   329    94.4 0.37  1.9                                  15    0       13,800   329    96.5 0.40  4.5                                  16    P       14,900   266    96.4 0.40  2.9                                  17    Q       12,700   326    96.5 0.41  3.5                                  18    R       11,500   303    96.1 0.39  4.6                                  19    D       27,600   673    95.6 0.42   0.81                                20    G       29,800   608    95.4 0.41  1.0                                  21    S        4,500    88    93.7 0.24  4.2                                  22    T        8,700   174    90.5 0.21  3.9                                  23    U        3,000   100    92.6 0.33  2.4                                  ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Particle  Application Example No.                                             size (μm)                                                                            4        7      10      15   24                                     ______________________________________                                        840 up    0.5      1.9    2.1     0.6  22.9                                   590 up    1.0      1.6    1.5     0.9  6.3                                    420 up    1.5      3.2    5.6     1.6  17.4                                   350 up    4.5      15.9   20.8    6.3  12.5                                   250 up    25.2     66.7   61.3    26.6 5.5                                    149 up    59.1     7.7    8.4     61.4 7.6                                     53 up    8.1      2.9    0.3     2.5  12.5                                    53 below 0.1      0.1    0.1     0.1  6.3                                    ______________________________________                                    

What is claimed is:
 1. A process for the polymerization of olefins whichcomprises polymerizing one or more olefins in the presence of a catalystcomprising(a) a titanium containing catalyst component obtained bycontacting(i) Component A, a magnesium dialkoxide soluble in inertsolvents represented by the formula Mg(OR) (OR¹) where R and R¹ are thesame or different branched alkyls or alkyl substituted cycloalkyls, eachR and R¹ having 7 or more carbon atoms. (ii) Component B, a siliconcompound having a hydrogen-silicon bond. (iii) Component C, an electrondonor compound, and (iiii) a titanium compound with the proviso thatComponent A, B and C are contacted with one another in an inert solventprior to contact with the titanium compound and (b) and organo metalcompound of Groups I-III metals of the Periodic Table.
 2. The process inaccordance with claim 1 wherein propylene is homopolymerized.
 3. Theprocess in accordance with claim 1 wherein propylene is randomlycopolymerized with ethylene.
 4. The process in accordance with claim 1wherein propylene is block polymerized with ethyene to form anethylene-propylene block copolymer.
 5. The process in accordance withclaim 1 wherein the silicon compound is selected from trichlorosilane,methyldichlorosilane and dimethylchlorosilane.
 6. The process inaccordance with claim 1 wherein the magnesium alkoxide is selected frommagnesium di-2-ethylhexyloxide, magnesium di-1-methylhexyloxide,magnesium di-1-ethylpentyloxide, magnesium di-1-methylheptyloxide andmagnesium di-1-ethylhexyloxide.
 7. The process in accordance with claim1 wherein the electron donor compound is selected from ethyl benzoate,diisobutylpthalate, benzoic acid anhydride, benzoyl chloride,diethylpthalate, pthalic acid-di-chloride, pthalic acid anhydride andn-butylmaleate.
 8. The process in accordance with claim 1 whereinComponent A is magnesium di-2-ethylhexyloxide, Component B istrichlorosilane and Component C is ethylbenzoate.
 9. The process inaccordance with claim 1 wherein the organo metal compound istriethylaluminum.
 10. The process in accordance with claim 1 furthercomprising an electron donor compound and/or an organosilicon compound.11. The process in accordance with claim 10 wherein the further electrondonor is selected from ethyl benzoate and ethyl-p-anisate.
 12. Theprocess in accordance with claim 10 wherein the further electron donorcompound is a sterically hindered electron donor compound.
 13. Theprocess in accordance with claim 12 wherein the further electron donorcompound is 2,2.6,6,-tetramethylpiperidine.
 14. THe process inaccordance with claim 10 wherein the organosilicon compound isphenyltriethoxysilane.